AU2009335226A1

AU2009335226A1 - Fungicidal compositions based on copper salts

Info

Publication number: AU2009335226A1
Application number: AU2009335226A
Authority: AU
Inventors: Lucio Filippini; Marilena Gusmeroli; Silvia Mormile; Matteo Santino Vazzola
Original assignee: Isagro SpA
Current assignee: Gowan Crop Protection Ltd
Priority date: 2009-01-02
Filing date: 2009-12-29
Publication date: 2011-07-28
Anticipated expiration: 2029-12-29
Also published as: ITMI20090001A1; BRPI0924197B1; JP2012514580A; UA106736C2; CA2748734A1; CN102307468A; CO6400169A2; IT1393328B1; US20110318427A1; EP2384117B1; RU2527307C2; US9204656B2; CN102307468B; WO2010076038A1; WO2010076038A8; KR20110108371A; KR101677307B1; AU2009335226B2; CA2748734C; PL2384117T3

Abstract

Fungicidal compositions are described, comprising: A) a copper salicylate having the following molecular formula (I) : CHOCu (HO) (I) wherein n represents 0, 1, 2 or 3; B) copper hydroxide Cu(OH)(H); C) a copper salt having the following formula (III) : 3Cu(OH)-X(Y)(III) wherein: X represents cupric ion Cuor calcium ion Ca; Y means chloride ion Cl or sulphate ion SO ; m is an integer equal to 1 or 2; optionally in the presence of dispersants, diluents, surfactants and/or co-formulants agronomically acceptable, and the relative agronomical formulations. The use of these fungicidal compositions and agronomical formulations for the control of phytopathogenic fungi in agricultural crops, is also described.

Description

WO 2010/076038 PCT/EP2009/009351 -1 FUNGICIDAL COMPOSITIONS BASED ON COPPER SALTS The present invention relates to compositions based on copper salts and their use for the control of phytopa thogenic fungi. 5 In particular, it relates to compositions based on copper salts capable of effectively controlling phytopa thogenic fungi causing damage to crops of economic inter est. Copper hydroxide, copper oxychloride, cuprocalcic 10 oxychloride, tribasic copper sulphate, Bordeaux mixture, are well-known active ingredients for being used indi vidually, or in a mixture with other fungicides, in foliar application for the control of phytopathogenic fungi. These copper active ingredients are described, for 15 example in "THE PESTICIDE MANUAL, 11th EDITION, BRITISH CROP PROTECTION COUNCIL, Pages 136, 268-270". In spite of the acknowledged effectiveness of copper products in the control of numerous fungal diseases which affect important agricultural crops, due to growing con 20 cern for the undesired toxicological effects that their prolonged use can cause, the necessity of reducing the rates of metallic copper within well-defined limits has become particularly important in recent years. European patent EP 1471787 describes fungicidal com 25 positions with which it is possible to reduce the doses of use of copper by mixing copper hydroxide with at least one other inorganic copper salt, such as copper oxychlo ride, tribasic copper sulphate, Bordeaux mixture, cupro- WO 2010/076038 PCT/EP2009/009351 -2 calcic oxychloride. However, the reduction of metallic copper content which can be obtained with these composi tions is still not satisfactory. The fungicidal range of action of these compositions is also limited to some 5 fungi belonging to the group of Oomycetes (Plasmopara viticola in particular). American patent US 4,075,326 describes fungicidal compositions in which inorganic copper salts are combined with copper salts of unsaturated dibasic organic acids. 10 In spite of the claimed enhancing effects, the use of these compositions does not at all seem to lead to an ac tual reduction in the copper doses. Example 4 of this document, for example, describes the improved fungicidal activity against Colletotrichum lagenarium of a composi 15 tion q consisting of 40% by weight of copper terephtha late (Cu content = 27.8%), 20% by weight of a wettable powder of copper oxychloride (Cu content = 41%), 40% by weight of a wettable powder of copper hydroxide (Cu con tent = 54%). This composition q therefore has a total 20 copper content equal to 27.8 x 0.4 + 41 x 0,2 + 54 x 0.4 = 40.92 % by weight. The fungicidal activity of the com position q is compared with the fungicidal activity of copper terephthalate alone (composition I-1), whose cop per content (27.8% by weight), is in fact lower than that 25 of the mixture of the composition q. Furthermore, the in crease in the activity observed for this ternary mixture with respect to the copper-organic product used alone, is in fact modest (10-20%), bearing in mind that the copper WO 2010/076038 PCT/EP2009/009351 -3 content of the composition q has an increase of 46% by weight. The "in vitro" antimicrobial activity of copper salts of salicylic acid with respect to phytopathogenic 5 fungi is also known, as described for example in "Pesti cides", 1980, 14(10), pages 29-30 and in "Indian Journal of Microbiology", 1981, pages 331-334. However, due to the reduced persistence, the occa sional appearance of phytotoxicity phenomena and the re 10 duced range of action, the practical use of these com pounds as fungicides is not completely satisfactory, even when associated with compounds capable of increasing their action as systemic acquired resistance inducers (SAR) with respect to fungal diseases in plants, as de 15 scribed in international patent application WO 2005/094580. The Applicant has now found ternary compositions comprising, in suitable ratios, a copper salicylate (in which the salicylic acid and copper are present in a mo 20 lar ratio of about 1:1), copper hydroxide, another copper salt selected from copper oxychloride, tribasic copper sulphate, Bordeaux mixture, cuprocalcic oxychloride, which overcome the drawbacks described above for the com positions according to the state of the art. In particu 25 lar, these ternary compositions show a surprisingly high fungicidal activity, which is exerted at a much lower dosage of copper than that of copper salicylate as such, and also with respect to that of the mixtures of inor- WO 2010/076038 PCT/EP2009/009351 -4 ganic copper salts described in European patent EP 1,471,787. These compositions also have a wider range of action and a more persistent efficacy, in addition to showing a reduced or null phytotoxicity which allows them 5 to be safely used on important crops. An object of the present invention therefore relates to fungicide compositions comprising: A) a copper salicylate having the following molecular formula (I): 10 C 7

H

4 0 3 Cu- (H 2 O)n (I) wherein n represents 0, 1, 2 or 3; B) copper hydroxide Cu(OH) 2 (II); C) a copper salt having the following formula (III): 3Cu(OH) 2 -X(Y)m (III) 15 wherein: - X represents cupric ion Cu2+ or calcium ion Ca2+; - Y means chloride ion Cl? or sulphate ion S0 4 2 - m is an integer equal to 1 or 2; optionally in the presence of dispersants, diluents, sur 20 factants and/or co-formulants agronomically acceptable. A further object of the present invention therefore relates to agronomical formulations comprising the above compositions and possible dispersants, diluents, surfac tants and/or co-formulants agronomically acceptable. 25 In particular, the compounds having formula (III) can be selected from copper oxychloride [3Cu(OH) 2 -CuC1 2 ], cuprocalcic oxychloride [3Cu(OH) 2 - CaCl 2 ], tribasic cop per sulphate [3 Cu (OH) 2 -CuSO 4 ], Bordeaux mixture WO 2010/076038 PCT/EP2009/009351 -5 [3Cu (OH) 2 -CaSO 4 ] Preferred compositions according to the present in vention are those in which the compounds having formula (I), (II) and (III) have an equivalent copper ratios re 5 spectively varying from 0.2:1:0.3 to 2:1:3, preferably from 0.4:1:0.8 to 1.2:1:1.2. Even more preferred compositions are those in which in the compound having formula (I) n represents 1 and the compounds having formula (I), (II) and (III) are present 10 in equivalent copper ratios respectively varying from 0.2:1:0.3 to 2:1:3, preferably from 0.4:1:0.8 to 1.2:1:1.2. Further preferred compositions are those in which in the compound having formula (I) n represents 1, the com 15 pound having formula (III) is copper oxychloride [3Cu(OH) 2 -CuCl 2 ] or tribasic copper sulphate [3Cu(OH) 2 CuSO 4 ] and the compounds having formula (I), (II) and (III) are present in equivalent copper ratios respec tively varying from 0.2:1:0.3 to 2:1:3, preferably from 20 0.4:1:0.8 to 1.2:1:1.2. Specific preferred compositions are: Cl: copper salicylate C 7

H

4 0 3 Cu-H 2 0 + copper hydroxide + copper oxychloride in equivalent copper ratio 1:1:1; C2: copper salicylate C 7

H

4 0 3 Cu-H 2 0 + copper hydroxide + 25 copper oxychloride in equivalent copper ratio 0.4:1:1; C3: copper salicylate C 7

H

4 0 3 Cu-H 2 0 + copper hydroxide + copper oxychloride in equivalent copper ratio 0.6:1:1; C4: copper salicylate C 7

H

4 0 3 Cu-H 2 0 + copper hydroxide + WO 2010/076038 PCT/EP2009/009351 -6 copper oxychloride in equivalent copper ratio 0.8:1:1; C5: copper salicylate C 7

H

4 0 3 Cu-H 2 0 + copper hydroxide + copper oxychloride in equivalent copper ratio 0.4:1:1.2; C6: copper salicylate C 7

H

4 0 3 Cu-H 2 0 + copper hydroxide + 5 copper oxychloride in equivalent copper ratio 0.8:1:1.2; C7: copper salicylate C 7

H

4 0 3 Cu-H 2 0 + copper hydroxide + copper oxychloride in equivalent copper ratio 1.2:1:0.8; C8: copper salicylate C 7

H

4 0 3 Cu-H 2 0 + copper hydroxide + copper oxychloride in equivalent copper ratio 2:1:0.3; 10 C9: copper salicylate C 7

H

4 0 3 Cu-H 2 0 + copper hydroxide + copper oxychloride in equivalent copper ratio 0.2:1:3; C10: copper salicylate C 7

H

4 0 3 Cu + copper hydroxide + cop per oxychloride in equivalent copper ratio 0.4:1:1; C11: copper salicylate C 7

H

4 0 3 Cu- + copper hydroxide + cop 15 per oxychloride in equivalent copper ratio 1:1:1; C12: copper salicylate C 7

H

4 0 3 Cu-H 2 O + copper hydroxide + tribasic copper sulphate in equivalent copper ratio 0.4:1:1; C13: copper salicylate C 7

H

4 0 3 Cu-H 2 0 + copper hydroxide + 20 tribasic copper sulphate in equivalent copper ratio 1:1:1; C14: copper salicylate C 7

H

4 0 3 Cu-H 2 0 + copper hydroxide + tribasic copper sulphate in equivalent copper ratio 0.7:1:1; 25 C15: copper salicylate C 7 H40 3 Cu-H 2 0 + copper hydroxide + Bordeaux mixture in equivalent copper ratio 1:1:1; C16: copper salicylate C 7

H

4 0 3 Cu-H 2 0 + copper hydroxide + cuprocalcic oxychloride in equivalent copper ratio 1:1:1; WO 2010/076038 PCT/EP2009/009351 -7 C17: copper salicylate C 7

H

4 0 3 Cu-2H 2 0 + copper hydroxide + copper oxychloride in equivalent copper ratio 1:1:1; C18: copper salicylate C 7

H

4 0 3 Cu-3H 2 0 + copper hydroxide + copper oxychloride in equivalent copper ratio 1:1:1. 5 The preparation of the compositions object of the present invention can be effected according to different methods, also depending on the fact that these composi tions only comprise copper salts, or are in the form of suitable agronomical formulations. 10 In the former case, the compositions according to the present invention are obtained by mechanically mixing suitable quantities of copper salicylate having formula (I), copper hydroxide (II) and copper salt having formula (III), already prepared individually. 15 The copper hydroxide (II) and copper salt having formula (III) are commercially available as technical products. The copper salicylate having formula (I) can be pre pared in various ways, for example by reacting salicylic 20 acid in an aqueous medium with a base and subsequently adding a soluble copper salt, such as, for example, cop per sulphate, or by reacting salicylic acid directly with a basic copper salt such as copper carbonate or copper hydroxide. 25 Alternatively, if the copper salt used for the preparation of the compound having formula (I) is copper hydroxide, the compositions of the present invention can be prepared by adding salicylic acid to copper hydroxide WO 2010/076038 PCT/EP2009/009351 -8 (II) in a suitable molar ratio and subsequently adding the copper salt having formula (III). Further, the compositions of the present invention can also be prepared by adding salicylic acid as such to 5 the mixture of copper hydroxide (II) and the copper salt having formula (III) in a suitable molar ratio. If the compositions are in the form of suitable agronomical formulations, they can be wettable powders, granules, granules dispersible in water, concentrated 10 suspensions, etc. They can be prepared either by formulating the cop per salts already mixed in suitable proportions together, or by mixing the salts formulated separately, in any or der. 15 Further, during the preparation of the formulations, salycilic acid as such can be added to the mixture of copper hydroxide (II) and the copper salt having formula (III), in a suitable molar ratio. Solid diluents which can be used in the formulations 20 are, for example: silica, kaolin, bentonite, talc, infu sorial earth, dolomite, calcium carbonate, magnesia, gyp sum, clays, synthetic silicates, attapulgite, seppiolite. Liquid diluents which can be used are, for example: water, aromatic or paraffinic organic solvents, alcohols, 25 esters, ketones, amides. Surfactants which can be used are, for example: salts of sodium, potassium, triethanolamine of alkyl naphthalenesulphonates, polynaphthalenesulphonates, WO 2010/076038 PCT/EP2009/009351 -9 phenyl sulphonates, polycarboxylates, sulfosuccinates, alkyl sulfosuccinates, alkyl sulphates, lignin sulpho nates, alkylaryl sulphonates; and again, polyethoxylated fatty alcohols, polyethoxylated alkylphenols, polyethoxy 5 lated esters of sorbitol, polypropoxy polyethoxylates (block polymers) can also be used. The compositions can also contain special additives for particular purposes, for example antifreeze agents such as propylene glycol, or adhesives such as Arabic 10 gum, polyvinyl alcohol, polyvinyl pyrrolidone, etc. In the phytosanitary formulations according to the present invention, the percentage content of equivalent metallic copper coming from the ternary mixture of copper salts having formula (I), (II) and (III) can vary from 3% 15 to 50%, preferably from 10% to 35%. As already specified, the compositions, object of the present invention, exert a surprisingly high fungi cidal activity, compared with the activities of the com ponents used individually. 20 A further object of the present invention therefore relates to the use of fungicidal compositions comprising: A) a copper salicylate having the following molecular formula (I):

C

7

H

4 0 3 Cu- (H 2 O)n (I) 25 wherein n represents 0, 1, 2 or 3; B) copper hydroxide Cu(OH) 2 (II); C) a copper salt having the following formula (III): 3Cu (OH) 2- X (Y) m (III) WO 2010/076038 PCT/EP2009/009351 -10 wherein: - X represents cupric ion Cu 2 + or calcium ion Ca 2 + - Y means chloride ion Cl or sulphate ion S0 4 ; - m is an integer equal to 1 or 2; 5 optionally in the presence of dispersants, diluents, sur factants and/or co-formulants agronomically acceptable, for the control of phytopathogenic fungi in agricultural crops. An object of the present invention also relates to a 10 method for the control of phytopathogenic fungi in agri cultural crops by the application of a fungicidal compo sition as previously defined. Examples of phytopathogenic fungi which can be ef fectively controlled with the fungicidal compositions or 15 with the agronomical formulations according to the pre sent invention are: Plasmopara viticola on vines, Phy tophthora spp. on vegetables, Pseudoperonospora cubensis on cucurbits, Peronospora tabacina on tobacco, Bremia lactucae on salads and spinach, Venturia spp. on fruit 20 trees, Uromyces appendiculatus on beans, Alternaria spp. on vegetables and fruit trees, Sphaeroteca fuliginea on cucurbits, Erysiphe spp. on vegetables and cereals. The compositions of the present invention can also be effectively used for the control of bacteria and phy 25 topathogenic viruses. The fungicidal compositions or phytosanitary formu lations according to the present invention can be used in agronomic practice for applications on plants or on a WO 2010/076038 PCT/EP2009/009351 -11 part of them, in particular on all parts of the plant, leaves, stems, branches and roots. The fungicidal compositions or phytosanitary formu lations according to the present invention can be conven 5 iently used in agronomic practice alone or, in order to broaden their range of action, in association with other fungicidal active ingredients. For illustrative purposes and without any limitative intent, some of the active ingredients which can be con 10 veniently used in a mixture with the compositions or for mulations object of the present invention, are listed hereunder: amisulbrom, benalaxyl, benalaxyl-M, benthiavalicarb isopropyl, captane, cyazofamid, cymoxanil, dinocap, 15 chlorotalonil, dimethomorph, ethaboxam, etridiazole, fa moxadone, fenamidone, fluazinam, flumorph, fluopicolide, folpet, fosetyl-aluminium, furalaxyl, hymenaxol, iprovalicarb, mandipropamid, metalaxyl, metalaxyl-M, ofurace, oxadixyl, pencicuron, procimidone, propamocarb, 20 prothiocarb, sulphur, tiram, tolclofos methyl, valifenalate (IR5885), zoxamide. The following examples are provided for illustrative and non-limiting purposes of the present invention. 25 EXAMPLE 1 Preparation of copper salicylate C 7

H

4 0 3 Cu-H 2 0 (I-1). 70.6 g (0.724 moles) of Cu(OH) 2 were added in por tions to a suspension of 100 g (0.724 moles) of salicylic WO 2010/076038 PCT/EP2009/009351 -12 acid in 1 litre of water, and the mixture was left under stirring at room temperature for 2 hours. The stirring system must be adequate in that, as the reaction proceeds and the pH increases to the final value of about 6, the 5 viscosity increases. The colour changes from green to ochre of the final product. The reaction mixture was then filtered on a buchner and dried in air, obtaining 148 g of the desired product (MW = 217.5). The reaction mixture can also be used as slurry 10 ready for the subsequent formulation (Example 7). Elemental analysis %: C = 38.85 (theoretical 38.71); H = 2.65 (theoretical 2.70); Cu = 29.10 (theoretical 29.2). EXAMPLE 2 Preparation of copper salicylate C 7

H

4 0 3 Cu-H 2 O (I-1). 15 A solution of NaOH, 58 g (1.45 moles) in 300 ml, was added to a suspension of 100 g (0.724 moles) of salicylic acid in 400 ml of water, until a complete dissolution was obtained. An aqueous solution of CuSO 4 , 180.8 g (0.724 moles) in 300 ml, was then added and the mixture was left 20 under stirring at room temperature for 8 hours. The stir ring system must be adequate in that, as the reaction proceeds and the pH increases to the final value of about 6, a fine green solid precipitates whose colour subse quently changes to ochre of the final product, and the 25 viscosity increases. The reaction mixture was then filtered on a buchner, washed with water (500 ml) and dried in air, obtaining 150 g of the desired product.

WO 2010/076038 PCT/EP2009/009351 -13 Elemental analysis %: C = 38.80 (theoretical 38.71); H = 2.60 (theoretical 2.70); Cu = 29.10 (theoretical 29.2). EXAMPLE 3 5 Preparation of the mixture copper salicylate C 7

H

4 0 3 Cu-H 2 0 (I-1) + copper hydroxide (II) in an equivalent copper ra tio of 1:1. 141.3 g (1.447 moles) of Cu(OH) 2 were added in por tions to a suspension of 100 g (0.724 moles) of salicylic 10 acid in 1 litre of water, and the mixture was left under stirring at room temperature for 4 hours. The reaction mixture was then filtered on a buchner and dried in air, obtaining 215 g of the desired product (elemental analy sis). 15 The reaction mixture can also be used as slurry ready for the subsequent formulation. EXAMPLE 4 Preparation of the composition Cl: copper salicylate

C

7

H

4 0 3 Cu-H 2 0 (I-1) + copper hydroxide (II) + copper oxy 20 chloride (III-1) in an equivalent copper ratio of 1:1:1. 70.6 g (0.724 moles) of Cu(OH) 2 were added in por tions to a suspension of 100 g (0.724 moles) of salicylic acid in 1.5 litres of water, and the mixture was left un der stirring at room temperature for 2 hours. The stir 25 ring system must be adequate in that, as the reaction proceeds and the pH increases to the final value of about 6, the viscosity increases. The colour changes from green to ochre of the final product. At this point, a further WO 2010/076038 PCT/EP2009/009351 -14 70.6 g (0.724 moles) of Cu(OH) 2 and 77.3 g (0.181 moles) of copper oxychloride 3Cu(OH) 2 -CuC1 2 (corresponding to 0.724 equivalents of copper), were added and the mixture was left under stirring for 30 minutes. The reaction mix 5 ture was then filtered on a buchner and dried in air, ob taining 290 g of the desired mixture (elemental analy sis). The reaction mixture can also be used as slurry ready for the subsequent formulation. 10 EXAMPLE 5 Preparation of the composition C2: copper salicylate

C

7

H

4 0 3 Cu-H 2 0 (I-1) + copper hydroxide (II) + copper oxy chloride (III-1) in an equivalent copper ratio of 0,4:1:1. 15 40 g (0.289 moles) of salicylic acid were added to a suspension of 98.8 g (1.014 moles) of Cu(OH) 2 and 77.3 g (0.181 moles) of copper oxychloride 3Cu(OH) 2 -CuC1 2 (cor responding to 0.724 equivalents of copper),in 1.5 litres of water; the mixture was left under stirring at room 20 temperature for 4 hours. The reaction mixture was then filtered on a buchner and dried in air, obtaining 192 g of the desired mixture (elemental analysis). The reaction mixture can also be used as slurry ready for the subsequent formulation. 25 EXAMPLE 6 Preparation of copper salicylate C 7

H

4 0 3 Cu-H 2 0 as a wet table powder (WP): I-1/WP A formulation of the wettable powder type was pre- WO 2010/076038 PCT/EP2009/009351 -15 pared by suitably mixing and grinding the following in gredients: INGREDIENTS QUANTITY % (wt/wt) 5 Technical copper salicylate at 99% 50.5 (Cu content = 29%) (equal to 14.6% of Cu) Sodium alkyl naphthalenesulphonate 1.5 10 Sodium polycarboxylate 1.0 Sodium ligninsulphonate 3.0 Silica 1.0 Calcium carbonate Complement to 100 15 EXAMPLE 7 Preparation of copper salicylate C 7

H

4 0 3 Cu-H 2 0 as dispersi ble granules (WG): I-1/WG 20 A formulation of the dispersible granule type, at 20% of copper (WG), was prepared by adding the following ingredients to the slurry obtained as described in Exam ple 1: WO 2010/076038 PCT/EP2009/009351 -16 INGREDIENTS QUANTITY (g) Sodium alkyl naphthalenesulphona- 2.3 te 5 Sodium polynaphthalenesulphonate 9.1 Calcium ligninsulphonate 11.4 Kaolin 48 10 The slurry thus prepared was granulated by evapora tion of the water present (fluid bed granulation), ob taining the final dispersible granule (WG) having the following composition: 15 INGREDIENTS QUANTITY % (wt/wt) Technical copper salicylate at 99% 69.0 (Cu content = 29%) (equal to 20% of Cu) 20 Sodium alkyl naphthalenesulphonate 1.0 Sodium polycarboxylate 4.0 Calcium ligninsulphonate 5.0 Kaolin Complement to 100 25 EXAMPLE 8 Preparation of the mixtures copper hydroxide + copper oxychloride in an equivalent copper ratio of 1:1, as a WO 2010/076038 PCT/EP2009/009351 -17 wettable powder (WP): CHCO-1/WP A formulation of the wettable powder type at 50% of copper (WP 50) was prepared by suitably mixing and grind ing the following ingredients: 5 INGREDIENTS QUANTITY % (wt/wt) Technical copper hydroxide at 93.7% 41.0 (Cu content = 61%) (equal to 25% of Cu) 10 Technical copper oxychloride at 96.6% 43.5 (Cu content = 57.5%) (equal to 25% of Cu) Sodium alkyl naphthalenesulphonate 1.5 15 Sodium polycarboxylate 1.0 Sodium ligninsulphonate 3.0 Silica 1.0 Calcium carbonate 9.0 20 EXAMPLE 9 Preparation of the mixture copper hydroxide + copper oxy chloride in an equivalent copper ratio of 1:1, as dis 25 persible granules (WG): CHCO-1/WG A formulation of the dispersible granule type at 50% of copper (WG) was prepared by suitably mixing, grinding and granulating the following ingredients: WO 2010/076038 PCT/EP2009/009351 -18 INGREDIENTS QUANTITY % (wt/wt) Technical copper hydroxide at 93.7% 41.0 5 (Cu content = 61%) (equal to 25% of Cu) Technical copper oxychloride at 96.6% 43.5 (Cu content = 57.5%) (equal to 25% of Cu) 10 Sodium alkyl naphthalenesulphonate 1.0 Sodium laurylsulphate 2.0 Sodium ligninsulphonate 8.0 Kaolin Complement to 100 15 EXAMPLE 10 Preparation of the composition C2: copper salicylate C7H 4 0 3 Cu-H 2 0 + copper hydroxide + copper oxychloride in an 20 equivalent copper ratio of 0.4:1:1, as a wettable powder (WP): C2/WP A formulation of the wettable powder type at 30% of copper (WP) was prepared by suitably mixing and grinding the following ingredients: WO 2010/076038 PCT/EP2009/009351 -19 INGREDIENTS QUANTITY % (wt/wt) Technical copper salicylate at 99% 17.2 5 (Cu content = 29%) (equal to 5% of Cu) Technical copper hydroxide at 93.7% 20.5 (Cu content = 61%) (equal to 12.5% of Cu) 10 Technical copper oxychloride at 96.6% 21.7 (Cu content = 57.5%) (equal to 12.5% of Cu) Sodium alkyl naphthalenesulphonate 1.5 15 Sodium polycarboxylate 1.0 Sodium ligninsulphonate 5.0 Silica 1.0 Calcium carbonate Complement to 100 20 Analogously, by suitably dosing the ratios of copper salicylate, copper hydroxide and copper oxychloride, a wettable powder formulation was prepared with copper at 25 30% of copper salicylate C 7

H

4 0 3 Cu-H 2 0 (I-1) + copper (II) hydroxide + copper (III-1) oxychloride in an equivalent copper ratio of 1:1:1; C1/WP.

WO 2010/076038 PCT/EP2009/009351 -20 EXAMPLE 11 Preparation of the composition Cl: copper salicylate

C

7

H

4 0 3 Cu-H 2 0 + copper hydroxide + copper oxychloride in an equivalent copper ratio of 1:1:1, as dispersible granules 5 (WG): C1/WG A further WG formulation was prepared as described in Example 8 starting from the following ingredients: INGREDIENTS QUANTITY % (wt/wt) 10 Technical copper salicylate at 99% 34.5 (Cu content = 29%) (equal to 10% of Cu) Technical copper hydroxide at 93.7% 16.4 15 (Cu content = 61%) (equal to 10% of Cu) Technical copper oxychloride at 96.6% 17.4 (Cu content = 57.5%) (equal to 10% of Cu) 20 Sodium alkyl naphthalenesulphonate 1.0 Sodium polynaphthalenesulphonate 4.0 Calcium ligninsulphonate 6.0 Calcium carbonate Complement to 100 25 EXAMPLE 12 Greenhouse preventive activity (7 days) against Plasmo- WO 2010/076038 PCT/EP2009/009351 -21 para viticola on vines. Vine leaves (cultivar Barbera), grown in a vase in a conditioned environment at 240C and at 60% of R.H. (Rela tive Humidity), were treated by spraying both sides with 5 the products being tested. 7 days after the treatment, the plants were inocu lated with an aqueous suspension of conidia of Plasmopara viticola (200.000 conidia/cc) by spraying the lower side with a compressed air gun. 10 After remaining 24 hours in a humidity-saturated en vironment at 210C, the plants were transferred for the incubation period (7 days) to a conditioned environment at 70% of R.H. and 21*C. After this period the external symptoms of the 15 pathogen appeared and it was therefore possible to pro ceed with an evaluation of the intensity of the infec tion, by means of a visual evaluation scale of the per centage of affected leaf area; the scale comprises the value 0 (healthy plant) and the value 100 (completely in 20 fected plant) as extremes. The Table indicates the results obtained for the following products/compositions: I-1/WP: wettable powder formulation at 50% (14.6 % of copper) of the copper salicylate C 7

H

4 0 3 Cu-H 2 0 (I-1) , de 25 scribed in Example 5; CHCO-1/WP: wettable powder formulation with copper at 50%, of copper hydroxide (II) + copper (III-1) oxychlo ride in an equivalent copper ratio of 1:1, described in WO 2010/076038 PCT/EP2009/009351 -22 Example 8; C1/WP: wettable powder formulation with copper at 30%, of copper salicylate C 7

H

4 0 3 Cu-H 2 0 (I-1) + copper hydroxide (II) + copper oxychloride (III-1) in an equivalent copper 5 ratio of 1:1:1, described in Example 10; C2/WP: wettable powder formulation with copper at 30%, of copper salicylate C 7

H

4 0 3 Cu-H 2 0 (I-1) + copper hydroxide (II) + copper oxychloride (III-1) in an equivalent cop per ratio of 0.4:1:1, described in Example 10; 10 The synergistic effect for the compositions was evaluated by comparing the activities obtained with those expected by both applying the Limpel formula, adapted to ternary mixtures, and also considering the additive ef fects of the components. 15 According to the Limpel formula ("Pesticide Science" (1987), vol. 19, pages 309-315): Eexp = E 1 + Er 1

+

11 - (E 1 xEri+r1/100) wherein: - Eexp is the fungicidal activity expected from a mixture 20 obtained by mixing component (I) at a dose D 1 and compo nents (II)+(III) at a dose Dr 1

+

1 r 1 ; - E 1 is the activity observed of component (I) when used alone at a dose DI; - Er 1 r+ 11 is the activity observed of the mixture (II) 25 (III) when used alone at a dose Dr 1

+

1 . Considering the additive effects: Eadd = E 1 + Er 1

+

1 ri A synergistic effect is present when the activities ob- WO 2010/076038 PCT/EP2009/009351 -23 served Eobs for the compositions are higher than those ex pected Eexp and Eadd From the results, it is evident the considerable in crease in the fungicidal activity obtained for the compo 5 sitions C1 and C2 with respect to the expected activi ties. The strong synergistic effect of compositions C1 and C2 is further confirmed by comparing the activities observed at 30 ppm copper rate for C1/WP, C2/WP, I-1/WP, CHCO-1/WP. 10 Table. Greenhouse preventive activity (7 days) against Plasmopara viticola on vines. Dose of Product Cu (ppm) Eobs Eexp Eadd 15 5 12 I-1/WP 10 18 30 36 20 35 CHCO-1/WP 25 42 20 30 56 C1/WP 30 100 46.7 53 C2/WP 30 100 49 54

Claims

1. Fungicidal compositions comprising: A) a copper salicylate having the following molecular formula (I): 5 C 7 H 4 0 3 Cu- (H 2 0)n (I) wherein n represents 0, 1, 2 or 3; B) copper hydroxide Cu(OH) 2 (II); C) a copper salt having the following formula (III): 3 Cu (OH) 2-X(Y)m (III) 10 wherein: - X represents cupric ion Cu2+ or calcium ion Ca 2 + ; - Y means chloride ion Cl~ or sulphate ion SO 4 2 - m is an integer equal to 1 or 2; optionally in the presence of dispersants, diluents, sur 15 factants and/or co-formulants agronomically acceptable.

2. Fungicidal compositions according to claim 1, charac terized in that the compounds of formulae (I), (II) and (III) exist in equivalent copper ratios ranging from 0.2:1:0.3 to 2:1:3, preferably from 0.4:1:0.8 to 20 1.2:1:1.2 respectively.

3. Fungicidal compositions according to claim 1, charac terized in that the compound of formula (I) has n equal to 1 and the compounds of formulae (I), (II) and (III) exist in equivalent copper ratios ranging from 0.2:1:0.3 25 to 2:1:3, preferably from 0.4:1:0.8 to 1.2:1:1.2, respec tively.

4. Fungicidal compositions according to claim 1, charac terized in that the compound of formula (I) has n equal WO 2010/076038 PCT/EP2009/009351 -25 to 1, the compound of formula (III) is copper oxychloride [3Cu(OH) 2 -CuC1 2 ] or tribasic copper sulphate [3Cu(OH) 2 -CuSO 4 ] and the compounds of formulae (I), (II) and (III) exist in equivalent copper ratios ranging from 5 0.2:1:0.3 to 2:1:3, preferably from 0.4:1:0.8 to 1.2:1:1.2, respectively.

5. Fungicidal compositions according to any one of claims 1 or 2, characterized in that they are selected from: - copper salicylate C 7 H 4 0 3 Cu-H 2 0 + copper hydroxide + cop 10 per oxychloride in equivalent copper ratio 1:1:1; - copper salicylate C 7 H 4 0 3 Cu-H 2 0 + copper hydroxide + cop per oxychloride in equivalent copper ratio 0.4:1:1; - copper salicylate C 7 H 4 0 3 Cu-H 2 0 + copper hydroxide + cop per oxychloride in equivalent copper ratio 0.6:1:1; 15 - copper salicylate C 7 H 4 0 3 Cu-H 2 0 + copper hydroxide + cop per oxychloride in equivalent copper ratio 0.8:1:1; - copper salicylate C 7 H 4 0 3 Cu-H 2 0 + copper hydroxide + cop per oxychloride in equivalent copper ratio 0.4:1:1.2; - copper salicylate C 7 H 4 0 3 Cu'H 2 O + copper hydroxide + cop 20 per oxychloride in equivalent copper ratio 0.8:1:1.2; - copper salicylate C 7 H 4 0 3 Cu-H 2 0 + copper hydroxide + cop per oxychloride in equivalent copper ratio 1.2:1:0.8; - copper salicylate C 7 H 4 0 3 Cu-H 2 0 + copper hydroxide + cop per oxychloride in equivalent copper ratio 2:1:0.3; 25 - copper salicylate C 7 H 4 0 3 Cu-H 2 0 + copper hydroxide + cop per oxychloride in equivalent copper ratio 0.2:1:3; - copper salicylate C 7 H 4 0 3 Cu + copper hydroxide + copper oxychloride in equivalent copper ratio 0.4:1:1; WO 2010/076038 PCT/EP2009/009351 -26 - copper salicylate C7H 4 0 3 Cu + copper hydroxide + copper oxychloride in equivalent copper ratio 1:1:1; - copper salicylate C 7 H 4 0 3 Cu-H 2 0 + copper hydroxide + tribasic copper sulphate in equivalent copper ratio 5 0.4:1:1; - copper salicylate C 7 H 4 0 3 Cu-H 2 0 + copper hydroxide + tribasic copper sulphate in equivalent copper ratio 1:1:1; - copper salicylate C 7 H 4 0 3 Cu-H 2 0 + copper hydroxide + 10 tribasic copper sulphate in equivalent copper ratio 0.7:1:1; - copper salicylate C 7 H 4 0 3 Cu-H 2 0 + copper hydroxide + Bor deaux mixture in equivalent copper ratio 1:1:1; - copper salicylate C 7 H 4 0 3 Cu-H 2 O + copper hydroxide + 15 cuprocalcic oxychloride in equivalent copper ratio 1:1:1; - copper salicylate C 7 H 4 0 3 Cu-2H 2 0 + copper hydroxide + copper oxychloride in equivalent copper ratio 1:1:1; - copper salicylate C 7 H 4 0 3 Cu-3H 2 0 + copper hydroxide + copper oxychloride in equivalent copper ratio 1:1:1. 20

6. Phytosanitary formulations comprising the fungicidal compositions according to any one of claims 1-5 and dis persants, diluents, surfactants and/or co-formulants agronomically acceptable.

7. Agronomical formulations according to claim 6, charac 25 terized in that they are wettable powders, granules, wa ter-dispersible granules or concentrated suspensions.

8. Agronomical formulations according to any one of claims 6 or 7, characterized in that they contain special WO 2010/076038 PCT/EP2009/009351 -27 additives such as antifreeze agents or adhesives.

9. Agronomical formulations according to any one of claims 6-8, characterized in that the equivalent percent age content of copper metal from the ternary mixture of 5 cupric salts of formulae (I) , (II) and (III) can range from 3% to 50%, preferably from 10% to 35%.

10. Use of fungicidal compositions comprising: A) a copper salicylate having the following molecular formula (I): 10 C 7 H 4 0 3 Cu- (H 2 0)n (I) wherein n represents 0, 1, 2 or 3; B) copper hydroxide Cu(OH) 2 (II); C) a copper salt having the following formula (III): 3Cu(OH) 2 -X(Y)m (III) 15 wherein: - X represents cupric ion Cu2+ or calcium ion Ca2+; - Y means chloride ion Cl- or sulphate ion SO 4 2 - m is an integer equal to 1 or 2; optionally in the presence of dispersants, diluents, sur 20 factants and/or co-formulants agronomically acceptable, for phytopathogenic fungi control in agricultural crops.

11. Use of fungicidal compositions according to any one of claims 2-5 for phytopathogenic fungi control in agri cultural crops. 25

12. Use of agronomical formulations according to any one of claims 6-9 for phytopathogenic fungi control in agri cultural crops.

13. Method for phytopathogenic fungi control in agricul- WO 2010/076038 PCT/EP2009/009351 -28 tural crops by applying a fungicidal composition as de fined in any of claims 1-5.